Cyan image forming method and silver halide color photographic material containing cyan coupler

Abstract

A silver halide color photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer containing at least one 1H-pyrrolo[2,1-c][1,2,4]triazole cyan coupler represented by the following general formula (I) or (II): ##STR1## wherein R 1 , R 2 and R 3 each represents a hydrogen atom or a substituent, provided that at least one of R 1 and R 2 is an electron withdrawing group which has a Hammett's substituent constant σp value of 0.15 or more; R 1 and R 2 may be bonded to form a ring; and X represents a hydrogen atom or a substituent capable of being released upon coupling with an oxidation product of an aromatic primary amine color developing agent; said coupler may form a bis-compound or or a polymer at R 1 , R 2 , R 3 or X; and a cyan image forming method comprising imagewise exposing a silver halide color photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer and subjecting the exposed photographic material to color development with an aromatic primary amine color dveloping agent at the presence of the above-described 1H-pyrrolo[2,1c][1,2,4]triazole cyan coupler.

What is claimed is: 
     
       1. A silver halide color photographic material comprising a support having thereon at least one red-sensitive silver halide emulsion layer containing at least one 1H-pyrrolo(2,1-c) (1,2,4)triazole cyan coupler represented by the following general formula (I) or (II): ##STR54## wherein R 1  and R 2  each is an electron withdrawing group which has a Hammett's substituent constant σp value of 0.15 to 1.0; R 1  and R 2  may be bonded to form a ring; R 3  represents an alkyl group, an aryl group, a cyano group, a carboxyl group, an amino group, an alkylamino group, an anilino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group or a thiocyanate group, and X represents a hydrogen atom or a substituent capable of being released upon coupling with an oxidation product of an aromatic primary amine color developing agent; said coupler may form a bis-compound or a polymer at R 1 , R 2 , R 3  or X. 
     
     
       2. A silver halide color photographic material as claimed in claim 1, wherein the Hammett's substituent constant σp value is 0.20 to 1.0. 
     
     
       3. A silver halide color photographic material as claimed in claim 2, wherein the electron withdrawing substituent has a Hammett's substituent constant σp value of 0.20 to 1.0 and is an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, nitro group, a dialkylphosphono group, a diarylphosphono group, a diarylphosphinyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxysulfonyl group, an aryloxysulfonyl group, an acylthio group, a sulfamoyl group, a thiocyanate group, an alkyl- or aryl-thiocarbonyl group, a halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with other electron withdrawing group having an σp value of not less than 0.20, a heterocyclic group, a chlorine atom, a bromide atom, an alkyl- or aryl-azo group or a selenocyanate group; these substituents may further have at least one substituent selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an alkyo- or aryl-sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl- or aryl-sulfonyl group, an alkyl- or aryl-sulfonyloxy group, an alkoxycarbonyl group, a heterocyclic oxy group, an alkyl- or aryl-azo group, an alkyl- or aryl-oxysulfonyl group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imido group, a selenocyanate group, a heterocyclic thio group, an alkyl- or aryl-sulfinyl group, a phosphinyl group, a phosphonyl group, a phosphono group, an aryloxycarbonyl group, an acyl group, an acylthio group, an azolyl group, an isocyanate, a thiocyanate group and an alkyl- or aryl-thiocarbonyl group. 
     
     
       4. A silver halide color photographic material as claimed in claim 1, wherein the Hammett's substituent constant σp value is 0.30 to 1.0. 
     
     
       5. A silver halide color photographic material as claimed in claim 4, wherein the electron withdrawing substituent has a Hammett's substituent constant σp value of 0.30 to 1.0 and is an acyl group, an acyloxy group, a carbamoyl group an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylthio group, an aryl group substituted with two or more other electron withdrawing substituents each having a Hammett's substituent constant σp value of 0.15 or more or a heterocyclic group; these substituents may further have at least one substituent selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an alkyo- or aryl-sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl- or aryl-sulfonyl group, an alkyl- or aryl-sulfonyloxy group, an alkoxycarbonyl group, a heterocyclic oxy group, an alkyl- or aryl-azo group, an alkyl- or aryl-oxysulfonyl group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imido group, a selenocyanate group, a heterocyclic thio group, an alkyl- or aryl-sulfinyl group, a phosphinyl group, a phosphonyl group, a phosphono group, n aryloxycarbonyl group, an acyl group, an acylthio group, an azolyl group, an isocyanate, a thiocyanate group and an alkyl- or aryl-thiocarbonyl group. 
     
     
       6. A silver halide color photographic material as claimed in claim 1, wherein the Hammett's substituent constant σp value is 0.60 to 1.0. 
     
     
       7. A silver halide color photographic material as claimed in claim 6, wherein the electron withdrawing substituent has a Hammett's substituent constant σp value of 0.60 to 1.0 and is a cyano group, a nitro group or an alkylsulfonyl group which may be further substituted with at least one substituent selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an alkyo- or aryl-sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl- or aryl-sulfonyl group, an alkyl- or aryl-sulfonyloxy group, an alkoxycarbonyl group, a heterocyclic oxy group, an alkyl- or aryl-azo group, an alkyl- or aryl-oxysulfonyl group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imido group, a selenocyanate group, a heterocyclic thio group, an alkyl- or aryl-sulfinyl group, a phosphinyl group, a phosphonyl group, a phosphono group, an aryloxycarbonyl group, an acyl group, an acylthio group, an azolyl group, an isocyanate, a thiocyanate group and an alkyl- or aryl-thiocarbonyl group. 
     
     
       8. A silver halide color photographic material as claimed in claim 1, wherein the Hammett's substituent constant σp value is 1.0 or less. 
     
     
       9. A silver halide color photographic material as claimed in claim 1, wherein the sum of the Hammett's substituent constant σp values of the electron withdrawing substituents represented by R 1  and R 2  is 1.8 or less. 
     
     
       10. A silver halide color photographic material as claimed in claim 1, wherein the electron withdrawing substituent having a Hammett's substituent constant σp value of 0.15 to 1.0 is an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, a diarylphosphono group, a diarylphosphinyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, an arylthio group, an alkyl or aryl-oxysulfonyl group, an acylthio group, a sulfamoyl group, an isocyanate group, a thiocyanate group, an alkyl- or aryl-thiocarbonyl group, a halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, a substituted aryl group, a heterocyclic group, a chlorine atom, a bromine atom, an alkyl- or aryl-azo group or a selenocyanate group; these substituents may further have at least one substituent selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an alkyo- or aryl-sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl- or aryl-sulfonyl group, an alkyl- or aryl-sulfonyloxy group, an alkoxycarbonyl group, a heterocyclic oxy group, an alkyl- or aryl-azo group, an alkyl- or aryl-oxysulfonyl group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imido group, a selenocyanate group, a heterocyclic thio group, an alkyl- or aryl-sulfinyl group, a phosphinyl group, a phosphonyl group, a phosphono group, an aryloxycarbonyl group, an acyl group, an acylthio group, an azolyl group, an isocyanate, a thiocyanate group and an alkyl- or aryl-thiocarbonyl group. 
     
     
       11. A silver halide color photographic material as claimed in claim 1, wherein the 1H-pyrrolo[2,1-c][1,2,4]-triazole cyan coupler is contained in an amount of 1×10 -3  to 1 mol per mol of light-sensitive silver halide. 
     
     
       12. A silver halide color photographic material as claimed in claim 1, wherein the 1H-pyrrolo[2,1-c][1,2,4]-triazole cyan coupler is capable of forming a cyan dye having a maximum wavelength in the range of from 600 to 700 nm. 
     
     
       13. A cyan image forming method comprising imagewise exposing a silver halide color photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer and subjecting the exposed photographic material to color development with an aromatic primary amine color developing agent in the presence of an 1H-pyrrolo(2,1-c)(1,2,4)triazole cyan coupler represented by the general formula (I) or (II): ##STR55## wherein R 1  and R 2  each represents a hydrogen atom or a substituent, provided that R 1  and R 2  each is an electron withdrawing group which has a Hammett's substituent constant σp value of 0.15 to 1.0; R 1  and R 2  may be bonded to form a ring; R 3  represents an alkyl group, an aryl group, a cyano group, a carboxyl group, an amino group, an alkylamino group, an anilino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group or a thiocyanate group, and X represents a hydrogen atom or a substituent capable of being released upon coupling with an oxidation product of an aromatic primary amine color developing agent; said coupler may form a bis-compound or a polymer at R 1 , R 2 , R 3  or X. 
     
     
       14. A cyan image forming method as claimed in claim 13, wherein the 1H-pyrrolo[2,1-c][1,2,4]triazole cyan coupler is incorporated in a color developing solution containing the aromatic primary amine color developing agent. 
     
     
       15. A cyan image forming method as claimed in claim 14, wherein the 1H-pyrrolo[2,1-c][1,2,4]triazole cyan coupler is incorporated in a color developing solution in an amount of from 0.0005 to 0.05 mol per liter of the color developing solution. 
     
     
       16. A cyan image forming method as claimed in claim 13, wherein 1H-pyrrolo[2,1-c][1,2,4]triazole cyan coupler is contained in the light-sensitive silver halide emulsion layer. 
     
     
       17. A cyan image forming method as claimed in claim 13, wherein the Hammett's substituent constant σp value is 0.20 to 1.0. 
     
     
       18. A cyan image forming method as claimed in claim 17, wherein the electron withdrawing substituent has a Hammett's substituent constant σp value of 0.20 to 1.0 and is an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, a diarylphosphono group, a diarylphosphinyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxysulfonyl group, an aryloxysulfonyl group, an acylthio group, a sulfamoyl group, a thiocyanate group, an alkyl- or aryl-thiocarbonyl group, a halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with other electron withdrawing group having the σp value of not less than 0.20, and a heterocyclic group, a chlorine atom, a bromine atom, an alkyl- or aryl-azo group or a selenocyanate group; these substituents may further have at least one substituent selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an alkyo- or aryl-sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl- or aryl-sulfonyl group, an alkyl- or aryl-sulfonyloxy group, n alkoxycarbonyl group, a heterocyclic oxy group, an alkyl- or aryl-azo group, an alkyl- or aryl-oxysulfonyl group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imido group, a selenocyanate group, a heterocyclic thio group, an alkyl- or aryl-sulfinyl group, a phosphinyl group, a phosphonyl group, a phosphono group, an aryloxycarbonyl group, an acyl group, an acylthio group, an azolyl group, an isocyanate, a thiocyanate group and an alkyl- or aryl-thiocarbonyl group. 
     
     
       19. A cyan image forming method as claimed in claim 13, wherein the Hammett's substituent constant σp value is 0.30 to 1.0. 
     
     
       20. A cyan image forming method as claimed in claim 13, wherein the Hammett's substituent constant σp value is 0.60 to 1.0. 
     
     
       21. A cyan image forming method as claimed in claim 20, wherein the electron withdrawing substituent has a Hammett's substituent constant σp value of 0.30 to 1.0 and is an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylthio group, an aryl group substituted with two or more other electron withdrawing substituents each having a Hammett's substituent constant σp value of 0.15 or more or a heterocyclic group; these substituents may further have at least one substituent selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, a n alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an alkyo- or aryl-sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl- or aryl-sulfonyl group, an alkyl- or aryl-sulfonyloxy group, an alkoxycarbonyl group, a heterocyclic oxy group, an alkyl- or aryl-azo group, an alkyl- or aryl- oxysulfonyl group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imido group, a selenocyanate group, a heterocyclic thio group, an alkyl- or aryl-sulfinyl group, a phosphinyl group, a phosphonyl group, a phosphono group, an aryloxycarbonyl group, an acyl group, an acylthio group, an azolyl group, an isocyanate, a thiocyanate group and an alkyl- or aryl-thiocarbonyl group. 
     
     
       22. A cyan image forming method as claimed in claim 20, wherein the electron withdrawing substituent has a Hammett's substituent constant σp value of 0.60 to 1.0 and is a cyano group, a nitro group and an alkylsulfonyl group which may be further substituted with at least one substituent selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an alkyo- or aryl-sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl- or aryl-sulfonyl group, an alkyl- or aryl-sulfonyloxy group, an alkoxycarbonyl group, a heterocyclic oxy group, an alkyl- or aryl-azo group, an alkyl- or aryl-oxysulfonyl group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imido group, a selenocyanate group, a heterocyclic thio group, an alkyl- or aryl-sulfinyl group, a phosphinyl group, a phosphonyl group, a phosphono group, an aryloxycarbonyl group, an acyl group, an acylthio group, an azolyl group, an isocyanate, a thiocyanate group and an alkyl- or aryl-thiocarbonyl group. 
     
     
       23. A cyan image forming method as claimed in claim 13, wherein at least R 1  is an electron withdrawing substituent which has a Hammett's substituent constant σp value of 0.15 or more. 
     
     
       24. A cyan image forming method as claimed in claim 13, wherein at least one of R 1  and R 2  is an electron withdrawing substituent having a Hammett's substituent constant σp value of 0.15 or more and the other of R 1  and R 2  is an electron withdrawing substituent. 
     
     
       25. A cyan image forming method as claimed in claim 13, wherein R 1  and R 2  each represents an electron withdrawing substituent having a Hammett's substituent constant σp value of 0.15 or more. 
     
     
       26. A cyan image forming method as claimed in claim 13, wherein R 1  and R 2  each represents an electron withdrawing substituent having a Hammett's substituent constant σp value of 0.20 or more. 
     
     
       27. A cyan image forming method as claimed in claim 20, wherein the sum of the Hammett's substituent constant σp values of the electron withdrawing substituents represented by R 1  and R 2  is 0.60 or more. 
     
     
       28. A cyan image forming method as claimed in claim 13, wherein the substituent represented by R 1  or R 2  is selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an alkyl- or aryl-sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl- or aryl-sulfonyl group, an alkyl- or aryl-sulfonyloxy group, an alkoxycarbonyl group, a heterocyclic oxy group, an alkyl- or aryl-azo group, an alkyl- or aryl-oxysulfonyl group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imido group, a selenocyanate group, a heterocyclic thio group, an alkyl- or aryl- sulfinyl group, a phosphinyl group, a phosphonyl group, a phosphono group, an aryloxycarbonyl group, an acyl group, an acylthio group, an azolyl group, an isocyanate, a thiocyanate group and an alkyl- or aryl-thiocarbonyl group; these groups may be further substituted with at least one of these substituents; R 1  and R 2  may be bonded to form a ring; and at least one of R 1  and R 2  is selected from these groups having a σp value of 0.15 or more. 
     
     
       29. A cyan image forming method as claimed in claim 13, wherein the electron withdrawing substituent having a Hammett's substituent constant σ value of 0.15 1.0 is an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, a diarylphosphono group, a diarylphosphinyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, an arylthio group, an alkyl- or aryl-oxysulfonyl group, an acylthio group, a sulfamoyl group, an isocyanate group, a thiocyanate group, an alkyl- or aryl-thiocarbonyl group, a halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, a substituted aryl group, a heterocyclic group, a chlorine atom, a bromine atom, an alkyl- or aryl-azo group or a selenocyanate group; these substituents may further have at least one substituent selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an alkyo- or aryl-sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl- or aryl-sulfonyl group, an alkyl- or aryl-sulfonyloxy group, an alkoxycarbonyl group, a heterocyclic oxy group, an alkyl- or aryl-azo group, an alkyl- or aryl-oxysulfonyl group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imido group, a selenocyanate group, a heterocyclic thio group, an alkyl- or aryl-sulfinyl group, a phosphinyl group, a phosphonyl group, a phosphono group, an aryloxycarbonyl group, an acyl group, an acylthio group, an azolyl group, an isocyanate, a thiocyanate group and an alkyl- or aryl-thiocarbonyl group. 
     
     
       30. A cyan image forming method as claimed in claim 13, wherein the 1H-pyrrolo[2,1-c][1,2,4]-triazole cyan coupler is capable of forming a cyan dye having a maximum wavelength in the range of from 600 to 700 nm.